CN1310714A - Substituted benzoylcyclohexandiones - Google Patents
Substituted benzoylcyclohexandiones Download PDFInfo
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- CN1310714A CN1310714A CN99809034A CN99809034A CN1310714A CN 1310714 A CN1310714 A CN 1310714A CN 99809034 A CN99809034 A CN 99809034A CN 99809034 A CN99809034 A CN 99809034A CN 1310714 A CN1310714 A CN 1310714A
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- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/06—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D239/08—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms directly attached in position 2
- C07D239/10—Oxygen or sulfur atoms
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- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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- A—HUMAN NECESSITIES
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- A—HUMAN NECESSITIES
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- A—HUMAN NECESSITIES
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- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
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- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/26—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings condensed with carbocyclic rings or ring systems
- C07D237/30—Phthalazines
- C07D237/32—Phthalazines with oxygen atoms directly attached to carbon atoms of the nitrogen-containing ring
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/08—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 condensed with carbocyclic rings or ring systems
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
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- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
- C07D285/13—Oxygen atoms
Abstract
The invention relates to substituted benzoylcyclohexandiones of general formula (I), wherein A represents a single bond or alkane diyl (alkene) and Z represents an optionally substituted 4-12 membered, saturated on unsaturated, monocylic or bicyclic, heterocyclic group containing 1-4 heteroatoms (up to 4 nitrogen atoms and optionally - alternatively or additively - an oxygen atom or a sulphur atom, or an SO group or an SO2 group) and which additionally contains one to three oxo groups (C=O) and/or thioxo groups as constituents of the heterocycle. The invention also relates to a method for producing said substituted benzoylcyclohexandiones and to the use thereof as herbicides.
Description
The invention relates to novel substituted benzoylcyclohexanediones, to their preparation and to their use as herbicides.
Certain substituted benzoylcyclohexanedionesare known to have herbicidal properties (cf. EP-A-090262, EP-A-135191, EP-A-186118, EP-A-186119, EP-A-186120, EP-A-319075, WO-A-96/26200, WO-A-97/46530, WO-A-99/07688). However, the activity of these compounds is not satisfactory in all respects.
The present invention accordingly provides novel substituted benzoylcyclohexanediones of the general formula (I)
Wherein
m represents the number 0, 1,2 or 3,
n represents the number 0, 1,2 or 3,
a represents a single bond or an alkanediyl (alkylene) group,
R1represents hydrogen, or represents in each case optionally substituted alkyl or alkoxycarbonyl,
R2represents optionally substituted alkyl, or with R1Together represent alkanediyl (alkylene), wherein in this case m represents 1 and R1And R2Either on the same carbon atom ("geminal") or on two adjacent carbon atoms ("vicinal"),
R3represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen or represents in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino or dialkylaminosulfonyl,
R4represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen or represents in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino or dialkylaminosulfonyl,
z represents an optionally substituted 4-to 12-membered saturated or unsaturated mono-or bicyclic heterocyclic group containing 1 to 4 heteroatoms (up to 4 nitrogen atoms and optionally either-orOr additionally- -an oxygen atom or a sulfur atom, or a SO group or SO2A group) and which additionally contains one to three oxo (C = O) and/or thioxo (C = S) groups as heterocyclic components,
including all possible tautomers of the compounds of general formula (I) and possible salts of the compounds of general formula (I).
In the above definitions, the hydrocarbon chain, such as alkyl or alkanediyl-, and when attached to a heteroatom, such as in alkoxy-may be straight-chain or branched.
In addition to the compounds of the general formula (I) mentioned above, it is also possible in each case for corresponding tautomers to be present-which are shown below by way of example.
Preferred substituents for the groups listed in the above formula are specified below:
m preferably represents the number 0, 1 or 2,
n preferably represents the number 0, 1 or 2,
a preferably represents a single bond or represents an alkanediyl (alkylene) group having 1 to 4 carbon atoms,
R1preferably represents hydrogen or optionally halogen-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulfinyl-or C1-C4-alkylsulfonyl-substituted alkyl having 1 to 6 carbon atoms or represents alkoxycarbonyl having up to 6 carbon atoms,
R2preferably represents optionally halogen-substituted alkyl having 1 to 6 carbon atoms, or with R1Together represent an alkanediyl (alkylene) group having 2 to 5 carbon atoms, wherein in this case m represents 1 and R1And R2Located on the same carbon atom ("harmonic") or on two adjacent carbon atoms ("vicinal"),
R3preferably represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen or represents in each case optionally halogen-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulfinyl-or C1-C4-alkylsulfonyl-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, each having up to 4 carbon atoms in the alkyl radicalOr alkylsulfonyl, or represents alkylamino, dialkylamino or di-alkylamino having in each case up to 4 carbon atoms in the alkyl radicalAn alkylaminosulfonyl group, an alkyl amino group,
R4preferably represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, or represents in each case optionally halogen-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulfinyl-or C1-C4-alkylsulfonyl-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each having up to 4 carbons in the alkyl radical, or represents alkylamino, dialkylamino or dialkylaminosulfonyl, each having up to 4 carbon atoms in the alkyl radical,
z represents one of the following heterocyclic groups:
wherein the dotted lines each represent a single bond or a double bond,
q represents oxygen or sulphur, and Q represents oxygen or sulphur,
R5represents hydrogen, hydroxy, mercapto, cyano, halogen, each optionally substituted by cyano, halogen-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulfinyl-or C1-C4-alkylsulfonyl-substituted alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl,each having at least 6 carbon atoms in the alkyl radical, represents allenylthio, represents alkylamino or dialkylamino, each optionally substituted by halogen, each having up to 6 carbon atoms in the alkyl radical, represents alkenyl, alkynyl, alkenyloxy, alkenylthio or alkenylamino, each optionally substituted by halogen, represents cycloalkyl, cycloalkyloxy, cycloalkylthio, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl radical and optionally having in the alkyl part up to 4 carbon atoms, each preferably substituted by halogenBase ofAlkylthio or cycloalkylalkylamino, or represents each optionally halogen-, C1-C4-alkyl-or C1-C4-alkoxy-substituted phenyl, phenoxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or benzylamino, representing pyrrolidino, piperidino or morpholino, or-at two adjacent radicals R5And R5In the case of a double bond- -to an adjacent radical R5Together also represent a benzo group, and
R6represents hydrogen, hydroxyl, amino, (1,1-) alkyleneamino having up to 4 carbon atoms, each optionally substituted by halogen-or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylamino, dialkylamino or alkanoylamino each having up to 6 carbon atoms in the alkyl radical, represents alkenyl, alkynyl or alkenyloxy each optionally substituted by halogen, represents cycloalkyl, cycloalkylalkyl or cycloalkylamino each optionally substituted by halogen, having 3 to 6 carbon atoms in the cycloalkyl radical and optionally having 3 carbon atoms in the alkyl moiety, or represents cycloalkyl, cycloalkylalkyl or cycloalkylamino each optionally substituted by halogen-, C1-C4-alkyl-or C1-C4-alkoxy-substituted phenyl or benzyl, or with an adjacent group R5Or R6Together represent optionally halogen-or C1-C4-an alkyl-substituted alkanediyl group having 3 to 5 carbon atoms,
wherein the individual radicals R5And R6If several of them are attached to the same heterocyclic group, they may have the same or different meanings as defined above.
A particularly preferably represents a single bond, methylene, ethylene (ethane-1, 1-diyl) and dimethylene (ethane-1, 2-diyl),
R1particularly preferably represents hydrogen, each of which is optionally substituted by fluorine-, chlorine-, methoxy-, ethoxy-, n-or isopropoxy-, methylthio-, ethylthio-, n-or isopropylthio-, methylsulfinyl-, ethylsulfinyl-, n-or isopropylsulfinyl-, methylsulphonyl-, ethylsulphonylAlkyl-, n-or isopropylsulfonyl-substituted methyl, ethyl, n-or isopropyl, n-, iso-, sec-or tert-butyl, or represents methoxycarbonyl, ethoxycarbonyl, n-or isopropoxycarbonyl.
R2Particularly preferably represents methyl, ethyl, n-or i-propyl, or with R1Together represent methylene, ethylene-1, 1-diyl (ethylene, -CH (CH)3) -), ethane-1, 2-diyl (dimethylene, -CH2CH2-), propane-1, 3-diyl (trimethylene group, -CH2CH2CH2-), but-1, 4-diyl (tetramethylene, -CH)2CH2CH2CH2-) or penta-1, 5-diyl (pentamethylene, -CH2CH2CH2CH2CH2-, where in this case m represents 1 and R1And R2At the same carbon atom ("gem") or at two adjacent carbon atoms ("vicinal"),
R3particularly preferably represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, iodine, in each case optionally substituted by fluorine-and/or chlorine-, methoxy-),Ethoxy-, n-or isopropoxy-, methylthio-, ethylthio-, n-or isopropylthio-, methylsulfinyl-, ethylsulfinyl-, methylsulphonyl-or ethylsulphonyl-substituted methyl, ethyl, n-or isopropyl, n-, iso-, sec-or tert-butyl, represents methoxy, ethoxy, n-or isopropoxy, each of which is optionally substituted by fluorine and/or chlorine-, methoxy-, ethoxy-, n-or isopropoxy, represents methylthio, ethylthio, n-or isopropylthio, methylsulphinyl, ethylsulfinyl, n-or isopropylsulfinyl, methylsulphonyl, ethylsulphonyl, n-or isopropylsulphonyl, each of which is optionally substituted by fluorine and/or chlorine, or represents methylamino, n-or isopropoxy, methyl, n-or, Ethylamino, n-or i-propylamino, dimethylamino, diethylamino, dimethylaminosulfonyl or diethylaminosulfonyl.
R4Particularly preferably nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, in each case optionally fluorine-and/or chlorine-, methoxyMethyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl which are substituted by yl-, ethoxy-, n-or i-propoxy-, methylthio-, ethylthio-, n-or i-propylthio-, methylsulfinyl-, ethylsulfinyl-, methylsulphonyl-or ethylsulphonyl, represents methoxy, ethoxy, n-or i-propoxy, each optionally substituted by fluorine-and/or chlorine-, methoxy-, ethoxy-, n-or i-propoxy, represents methylthio, ethylthio, n-or i-propylthio, methylsulfinyl, ethylsulfinyl, n-or i-propylsulfinyl, methylsulphonyl, ethylsulphonyl, n-or i-propylsulphonyl, each optionally substituted by fluorine-and/or chlorine-and, or represents methylamino, ethylamino, n-or i-propylamino, dimethylamino, diethylamino, dimethylaminosulfonyl or diethylaminosulfonyl.
Z particularly preferably represents the following heterocyclyl group
R5Particularly preferably represents hydrogen, hydroxyl, mercapto, cyano, fluorine, chlorine, bromine, iodine, represents methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, methylsulfinyl, ethylsulfinyl, n-or i-propylsulfinyl, n-, i-, s-or t-butylthio, methylsulfinyl, ethylsulfinyl, n-or i-propylsulfinyl, methylsulphonyl, ethylsulphonyl, n-or i-propylsulphonyl-substituted methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, methoxy, ethoxy, n-butylOr isopropoxy, n-, i-, s-or t-butoxy, methylthio, ethylthio, n-or i-propylthio, n-, i-, s-or t-butylthio, methylsulfinyl, ethylsulfinyl, n-or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n-or i-propylsulfonyl, or represents methylamino, ethylamino, n-or i-propylamino, n-, i-, s-or t-butylamino, dimethylamino, diethylamino, di-n-propylamino or diisopropylamino, represents in each case optionally fluorine-and/or chlorine-substituted vinyl, propenyl, butenyl, ethynyl, propynyl, butynylPropenyloxy, butenyloxy, propenylthio, butenylthio, propenylamino or butenylamino, each being optionally substituted by fluoro-and/or chloro-cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopropylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino or cyclohexylmethylamino, or each being optionally substituted by fluoro-or chloro-amino, Chloro-, methyl-, ethyl-, n-or isopropyl-, n-, i-, s-or t-butyl-, methoxy-, ethoxy-, n-or i-propoxy-substituted phenyl, phenoxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or benzylamino, or- -in two adjacent radicals R5And R5In the case of a double bond- -also with an adjacent R5Together represent a benzo group, which is,
R6particularly preferably represents hydrogen, hydroxyl, amino, represents methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, methoxy, ethoxy, n-or i-propoxy, methylamino, ethylamino or dimethylamino, each of which is optionally substituted by fluorine and/or chlorine, represents vinyl, propenyl, ethynyl, propynyl or propenyloxy, represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally substituted by fluorine and/or chlorine, or represents each of which is optionally substituted by fluorine, chlorine, methyl, ethyl, n-or i-propyl, n-, or i-propyl, Iso-, sec-or tert-butyl-, methoxy-, ethoxy-, n-or isopropoxy-substituted phenyl or benzyl, or R adjacent thereto5Or R6Together represent each optionally methyl-and/or ethyl-substituted propane-1, 3-diyl (trimethylene) and butane-1, 4-diyl (tetradiyl)Methylene) or penta-1, 5-diyl (pentamethylene),
wherein the individual radicals R5And R6If several of them are attached to the same heterocyclic group, they may have the same or different meanings as defined above.
A very particularly preferably represents a single bond or represents methylene,
R1very particularly preferably represents hydrogen, methyl, ethyl, n-or i-propyl.
R2Very particularly preferably represents a methyl group,
R3very particularly preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl,
R4very particularly preferably represents nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl.
R5Very particularly preferably represents hydrogen, hydroxyl, chlorine, bromine, methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, fluoroethyl, chloroethyl, difluoroethyl, dichloroethyl, fluoro-n-propyl, fluoroisopropyl, chloro-n-propyl, chloroisopropyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methoxy, ethoxy, n-or i-propoxy, n-, i-, s-or t-butoxy, fluoroethoxy, chloroethoxy, difluoroethoxy, dichloroethoxy, trifluoroethoxy, trichloroethoxy, fluoroethoxyA phenyl group, a chlorofluoroethoxy group, a chlorodifluoroethoxy group, a fluorodichloroethoxy group, a methylthio group, an ethylthio group, a n-or isopropylthio group, a fluoroethylthio group, a chloroethylthio group, a difluoroethylthio group, a dichloroethylthio group, a chlorofluoroethylthio group, a chlorodifluoroethylthio group, a fluorodichloroethylthio group, a methylsulfinyl group, an ethylsulfinyl group, a n-or isopropylsulfinyl group, a methylsulfonyl group, an ethylsulfonyl group, a n-or isopropylsulfonyl group, a dimethylamino group, a propenylthio group, a butenylthio group, a propynylthio group, a butynylthio group, a cyclopropyl group, a cyclopropylmethyl group, a.
R6Very particularly preferably represents amino, methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, methoxy, ethoxy, methylamino, dimethylamino, cyclopropyl or cyclopropylmethyl, or with R5Together represent propane-1, 3-diyl (trimethylene), butane-1, 4-diyl (tetramethylene) or pentane-1, 5-diyl (pentamethylene).
A most preferably represents methylene.
The present invention preferably provides wherein m, n, A, R1、R2、R3、R4And Z are each as defined aboveSodium, potassium, magnesium, calcium, ammonium, C of the compound of formula (I)1-C4Alkyl ammonium, di- (C)1-C4-alkyl) -ammonium, tri- (C)1-C4Alkyl) -ammonium, tetra- (C)1-C4-alkyl) -ammonium, tri- (C)1-C4-alkyl) -sulfonium, C5Or C6Cycloalkylammonium and di- (C)1-C2-alkyl) -benzylammonium salts.
Preference is given according to the invention to compounds of the formula (I) in which there are combinations of the preferred meanings mentioned above.
Particular preference is given according to the invention to compounds of the formula (I) in which there are combinations of the meanings mentioned as being particularly preferred.
Very particular preference is given according to the invention to compounds of the formula (I) in which a combination of the meanings mentioned above as being very particularly preferred is present.
The following compounds of the general formulae (IA), (IB) and (IC) are particular to the inventionTo be emphasized:
wherein
m represents the number 0, 1 or 2,
n represents the number 0, 1 or 2,
a particularly preferably represents a single bond or represents methylene,
q represents oxygen or sulphur, and Q represents oxygen or sulphur,
R1represents hydrogen, methyl, ethyl, n-or isopropyl,
R2represents a methyl group, and a salt thereof,
R3represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl,
R4represents nitro, cyano, fluoro, chloro, bromo, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulphonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl or dimethylaminosulphonyl.
R5Represents hydrogen, hydroxy, chloro, bromo, methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, fluoroethyl, chloroethyl, difluoroethyl, dichloroethyl, fluoro-n-propyl, fluoroisopropyl, chloro-n-propyl, chloroisopropyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methoxy, ethoxy, n-or i-propoxy, n-, i-, s-or t-butoxy, fluoroethoxy, chloroethoxy, difluoroethoxy, dichloroethoxy, methoxyEthoxy, trifluoroethoxy, trichloroethoxy, chlorofluoroethoxy, chlorodifluoroethoxy, fluorodichloroethoxy, methylthio, ethylthio, n-or isopropylthio, fluoroethylthio, chloroethylthio, difluoroethylthio, dichloroethylthio, chlorofluoroethylthio, chlorodifluoroethylthio, fluorodichloroethylthio, methylsulfinyl, ethylsulfinyl, n-or isopropylsulfinyl, methylsulfonyl, ethylsulfonyl, n-or isopropylsulfonyl, dimethylamino, propenylthio, butenylthio, propynylthio, butynylthio, cyclopropyl, cyclopropylmethyl, cyclopropylmethoxy, phenyl or phenoxy, and
R6represents amino, methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, methoxy, ethoxy, methylamino, dimethylamino, cyclopropyl or cyclopropylmethyl, or with R5Together represent propane-1, 3-diyl (trimethylene), butane-1, 4-diyl (tetramethylene) or pentane-1, 5-diyl (pentamethylene).
Here, particular emphasis is given to compounds of the formula (IA) in which A represents methylene.
The general or preferred radical definitions mentioned above apply to the end products of the formula (I) and, correspondingly, also to the starting materials or intermediates required in each case for the preparation. These radical definitions may be combined with one another as desired, i.e. including combinations between the preferred ranges mentioned above.
Examples of compounds of general formula (I) according to the invention are listed below.
Group 1
Herein, R is3、(R4)n、R5And R6Each having the meaning given in the table below, for example:
Group 2
Herein, R is3、(R4)n、R5And R6Each having the meaning given in the table below, for example:
Group 3
Herein, R is3、(R4)n、R5And R6Each having the meaning given in group 1.
| R3 | (position) (R)4)n | R5 | R6 |
| H | - | CF3 | CH3 |
| F | - | CF3 | CH3 |
| Cl | - | CF3 | CH3 |
| Br | - | CF3 | CH3 |
| I | - | CF3 | CH3 |
| NO2 | - | CF3 | CH3 |
| CN | - | CF3 | CH3 |
| CH3 | - | CF3 | CH3 |
| OCH3 | - | CF3 | CH3 |
| R3 | (position-) (R4)n | R5 | R6 |
| CF3 | - | CF3 | CH3 |
| OCHF2 | - | CF3 | CH3 |
| OCF3 | - | CF3 | CH3 |
| SO2CH3 | - | CF3 | CH3 |
| H | - | OCH3 | CH3 |
| F | - | OCH3 | CH3 |
| Cl | - | OCH3 | CH3 |
| Br | - | OCH3 | CH3 |
| I | - | OCH3 | CH3 |
| NO2 | - | OCH3 | CH3 |
| CN | - | OCH3 | CH3 |
| CH3 | - | OCH3 | CH3 |
| OCH3 | - | OCH3 | CH3 |
| CF3 | - | OCH3 | CH3 |
| OCHF2 | - | OCH3 | CH3 |
| OCF3 | - | OCH3 | CH3 |
| SO2CH3 | - | OCH3 | CH3 |
| H | - | SCH3 | CH3 |
| F | - | SCH3 | CH3 |
| Cl | - | SCH3 | CH3 |
| Br | - | SCH3 | CH3 |
| I | - | SCH3 | CH3 |
| NO2 | - | SCH3 | CH3 |
| CN | - | SCH3 | CH3 |
| CH3 | - | SCH3 | CH3 |
| OCH3 | - | SCH3 | CH3 |
| CF3 | - | SCH3 | CH3 |
| OCHF2 | - | SCH3 | CH3 |
| OCF3 | - | SCH3 | CH3 |
| R3 | (position) (R)4)n | R5 | R6 |
| Cl | (3-)Cl | CF3 | CH3 |
| NO2 | (3-)Cl | CH3 | CH3 |
| Cl | (3-)Cl | SCH3 | CH3 |
| CH3 | (3-)Cl | Cl | CH3 |
| OCH3 | (3-)Cl | OCH3 | CH3 |
| CF3 | (3-)Cl | CF3 | CH3 |
| OCHF2 | (3-)Cl | CH3 | CH3 |
| OCF3 | (3-)Cl | CH3 | CH3 |
| SO2CH3 | (3-)Cl | OCH3 | CH3 |
| R3 | (position-) (R4)n | R5 | R6 |
| Cl | (2-)Cl | CF3 | CH3 |
| Cl | (2-)Cl | SCH3 | CH3 |
| Cl | (2-)Cl | SC2H5 | CH3 |
| Cl | (2-)Cl | SC3H7 | CH3 |
| Cl | (2-)Cl | SC3H7-i | CH3 |
| R3 | (position-) (R4)n | R5 | R6 |
| Cl | (2-)SO2CH3 | SC2H5 | OCH3 |
| Cl | (2-)SO2CH3 | OCH3 | OCH3 |
| Cl | (2-)SO2CH3 | OC2H5 | OCH3 |
| Cl | (2-)SO2CH3 | CH3 | OC2H5 |
| Cl | (2-)SO2CH3 | C2H5 | OC2H5 |
| Cl | (2-)SO2CH3 | C3H7 | OC2H5 |
| Cl | (2-)SO2CH3 | SCH3 | OC2H5 |
| Cl | (2-)SO2CH3 | SC2H5 | OC2H5 |
| Cl | (2-)SO2CH3 | OCH3 | OC2H5 |
| Cl | (2-)SO2CH3 | OC2H5 | OC2H5 |
| SO2CH3 | (2-)Cl | Cl | OCH3 |
| SO2CH3 | (2-)Cl | Br | OCH3 |
| SO2CH3 | (2-)Cl | CH3 | OCH3 |
| SO2CH3 | (2-)Cl | C2H5 | OCH3 |
| SO2CH3 | (2-)Cl | C3H7 | OCH3 |
| SO2CH3 | (2-)Cl | SCH3 | OCH3 |
| SO2CH3 | (2-)Cl | SC2H5 | OCH3 |
| SO2CH3 | (2-)Cl | OCH3 | OC2H5 |
| SO2CH3 | (2-)Cl | OC2H5 | OC2H5 |
| SO2CH3 | (2-)Cl | CH3 | OC2H5 |
| SO2CH3 | (2-)Cl | C2H5 | OC2H5 |
| SO2CH3 | (2-)Cl | C3H7 | OC2H5 |
| SO2CH3 | (2-)Cl | SCH3 | OC2H5 |
| SO2CH3 | (2-)Cl | SC2H5 | OC2H5 |
| SO2CH3 | (2-)Cl | OCH3 | OC2H5 |
| CF3 | (2-)Cl | Br | CH3 |
| CF3 | (2-)Cl | SCH3 | CH3 |
| CF3 | (2-)Cl | OCH3 | CH3 |
| CF3 | (2-)Cl | N(CH3)2 | CH3 |
| R3 | (position-) (R4)n | R5 | R6 |
| CF3 | (2-)Cl | CF3 | CH3 |
| CF3 | (2-)NO2 | Br | CH3 |
| CF3 | (2-)NO2 | SCH3 | CH3 |
| CF3 | (2-)NO2 | OCH3 | CH3 |
| CF3 | (2-)NO2 | N(CH3)2 | CH3 |
| CF3 | (2-)NO2 | CF3 | CH3 |
| CF3 | (2-)CH3 | Br | CH3 |
| CF3 | (2-)CH3 | SCH3 | CH3 |
| CF3 | (2-)CH3 | OCH3 | CH3 |
| CF3 | (2-)CH3 | N(CH3)2 | CH3 |
| CF3 | (2-)CH3 | CF3 | CH3 |
| CF3 | (2-)OCH3 | Br | CH3 |
| CF3 | (2-)OCH3 | SCH3 | CH3 |
| CF3 | (2-)OCH3 | OCH3 | CH3 |
| CF3 | (2-)OCH3 | N(CH3)2 | CH3 |
| CF3 | (2-)OCH3 | CF3 | CH3 |
| SO2CH3 | (2-)NO2 | Br | CH3 |
| SO2CH3 | (2-)NO2 | SCH3 | CH3 |
| SO2CH3 | (2-)NO2 | OCH3 | CH3 |
| SO2CH3 | (2-)NO2 | N(CH3)2 | CH3 |
| SO2CH3 | (2-)NO2 | CF3 | CH3 |
| SO2CH3 | (2-)CF3 | Br | CH3 |
| SO2CH3 | (2-)CF3 | SCH3 | CH3 |
| SO2CH3 | (2-)CF3 | OCH3 | CH3 |
| SO2CH3 | (2-)CF3 | N(CH3)2 | CH3 |
| SO2CH3 | (2-)CF3 | CF3 | CH3 |
| SO2CH3 | (2-)SO2CH3 | Br | CH3 |
| SO2CH3 | (2-)SO2CH3 | SCH3 | CH3 |
| SO2CH3 | (2-)SO2CH3 | OCH3 | CH3 |
| R3 | (position-) (R4)n | R5 | R6 |
| SO2CH3 | (2-)SO2CH3 | N(CH3)2 | CH3 |
| SO2CH3 | (2-)SO2CH3 | CF3 | CH3 |
| CN | (2-)Cl | Br | CH3 |
| CN | (2-)Cl | SCH3 | CH3 |
| CN | (2-)Cl | OCH3 | CH3 |
| CN | (2-)Cl | N(CH3)2 | CH3 |
| CN | (2-)Cl | CF3 | CH3 |
| CN | (2-)NO2 | Br | CH3 |
| CN | (2-)NO2 | SCH3 | CH3 |
| CN | (2-)NO2 | OCH3 | CH3 |
| CN | (2-)NO2 | N(CH3)2 | CH3 |
| CN | (2-)NO2 | CF3 | CH3 |
| CN | (2-)CF3 | Br | CH3 |
| CN | (2-)CF3 | SCH3 | CH3 |
| CN | (2-)CF3 | OCH3 | CH3 |
| CN | (2-)CF3 | N(CH3)2 | CH3 |
| CN | (2-)CF3 | CF3 | CH3 |
| CN | (2-)SO2CH3 | Br | CH3 |
| CN | (2-)SO2CH3 | SCH3 | CH3 |
| CN | (2-)SO2CH3 | OCH3 | CH3 |
| CN | (2-)SO2CH3 | N(CH3)2 | CH3 |
| CN | (2-)SO2CH3 | CF3 | CH3 |
| Br | (2-)NO2 | Br | CH3 |
| Br | (2-)NO2 | SCH3 | CH3 |
| Br | (2-)NO2 | OCH3 | CH3 |
| Br | (2-)NO2 | N(CH3)2 | CH3 |
| Br | (2-)NO2 | CF3 | CH3 |
| Br | (2-)CF3 | Br | CH3 |
| Br | (2-)CF3 | SCH3 | CH3 |
| R3 | (position-) (R4)n | R5 | R6 |
| Br | (2-)CF3 | OCH3 | CH3 |
| Br | (2-)CF3 | N(CH3)2 | CH3 |
| Br | (2-)CF3 | CF3 | CH3 |
| Br | (2-)SO2CH3 | Br | CH3 |
| Br | (2-)SO2CH3 | SCH3 | CH3 |
| Br | (2-)SO2CH3 | OCH3 | CH3 |
| Br | (2-)SO2CH3 | N(CH3)2 | CH3 |
| Br | (2-)SO2CH3 | CF3 | CH3 |
| Br | (2-)CH3 | Br | CH3 |
| Br | (2-)CH3 | SCH3 | CH3 |
| Br | (2-)CH3 | OCH3 | CH3 |
| Br | (2-)CH3 | N(CH3)2 | CH3 |
| Br | (2-)CH3 | CF3 | CH3 |
Group 4
Herein, R is3、(R4)n、R5And R6Each having the meaning given in group 2.
Novel substituted benzoylcyclohexanediones of the general formula (I) have strong and selective herbicidal activity.
Novel substituted benzoylcyclohexanediones of the general formula (I) are obtained as follows:
if appropriatein the presence of a dehydrating agent, if appropriate in the presence of one or more reaction auxiliaries and if appropriate in the presence of a diluent, with 1, 3-cyclohexanediones of the general formula (II) or derivatives thereof
Wherein
m、R1And R2As defined above
With substituted benzoic acids of the general formula (III)
Wherein
n、A、R3、R4And Z are each as defined above, and,
and, if appropriate, the compounds of the formula (I) obtained in this way are subsequently subjected to electrophilic or nucleophilic or oxidation or reduction reactions in the range defined by the substituents by customary methods or are converted into salts by customary methods.
The compounds of formula (I) may be converted to other compounds of formula (I) as defined above by conventional means, for example by meta-nucleophilic substitution (e.g. R)5:Cl→OC2H5、SCH3) Or by oxidation (e.g. R)5: )。
In principle, the compounds of general formula (I) can also be synthesized using the reaction scheme shown below:
reacting a 1, 3-cyclohexanedione of the general formula (II) or a derivative thereof- -above- -with a reactive derivative of a substituted benzoic acid of the general formula (III) - -above- -in particular with the corresponding acid chloride, carboxylic anhydride, acyl cyanide, carboxylic acid methyl ester or carboxylic acid ethyl ester thereof- -if appropriate in the presence of a reaction auxiliary such as triethylamine (and if appropriate additionally zinc chloride) and if appropriate in the presence of a diluent such as dichloromethane:
(Y is, for example, CN, Cl),
In addition to the desired C-benzoylation in cyclohexanediones, there are also O-benzoylation reactions in the reactions outlined above for the preparation of the general formulA (I) -see, for example, the following reaction schemes (cf. for example Synthesis [ Sythesis]1978, 925-927; Tetrahedron letters 37(1996),1007-1009, WO-A-91/05469). However, the O-benzoyl compound formed in this process isomerizes under the reaction conditions of the process of the invention to the C-benzoyl compound of the formula (I).
Using, for example, 1, 3-cyclohexanedione and 2- (3-carboxy-5-fluorobenzyl) -5-ethyl-4-methoxy-2, 4-dihydro-3H-1, 2, 4-triazol-3-one as starting materials, the reaction route of the process of the invention can be illustrated by the following reaction scheme:
formula (II) provides a general definition of cyclohexanediones used as starting materials in the process for preparing the compounds of formula (I) according to the invention. In the formula (II), m and R1And R2Each preferably having m, R already mentioned above in connection with the description of the compounds of the formula (I) according to the invention1And R2Preferred, particularly preferred or very particularly preferred meanings of (b).
The starting materials of the formula (II) are known and/or can be prepared by methods known per se.
The general formula (III) provides a general definition of a further substituted benzoic acid usedas starting material in the process according to the invention. In the formula (III), n, A, R3、R4And Z each preferably has n, A, R already mentioned above in connection with the description of the compounds of the formula (I) according to the invention3、R4And the preferred, particularly preferred, very particularly preferred or most preferred meanings of Z.
Except that 2- (5-carboxy-2, 4-dichloro-phenyl) -4-difluoromethyl-5-methyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one, also known as 2, 4-dichloro-5- (4-difluoromethyl-4, 5-dihydro-3-methyl-5-oxo-1H-1, 2, 4-triazol-1-yl) -benzoic acid (CAS registry No. 90208-77-8) and 2- (5-carboxy-2, 4-dichloro-phenyl) -4, 5-dimethyl-2, 4-dihydro-3H-1, starting materials of the general formula (III), which are 2, 4-triazol-3-ones, also known as 2, 4-dichloro-5- (4, 5-dihydro-3, 4-dimethyl-5-oxo-1H-1, 2, 4-triazol-1-yl) -benzoic acid (CA accession number 90208-76-7), have hitherto not been disclosed in the literature. Apart from 2- (5-carboxy-2, 4-dichloro-phenyl) -4-difluoromethyl-5-methyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one and 2- (5-carboxy-2, 4-dichloro-phenyl) -4, 5-dimethyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one (cf. JP-A-58225070- -cited in chemical Abstract 100:209881, JP-A02015069- -cited in chemical Abstract 113: 23929), they likewise form the subject-matter of the present application as new compounds.
The novel substituted benzoic acids of the general formula (III) are obtained as follows:
the benzoic acid derivatives of the general formula (IV) are reacted with water in the presence of a hydrolysis assistant such as sulfuric acid at a temperature of 50 to 120 ℃ (see, preparation examples)Wherein
n、A、R3And R4And Z are each as defined above, and
y represents cyano, carbamoyl, halogenocarbonyl or alkoxycarbonyl,
the benzoic acid derivatives of the general formulｃA (IV) required as precursors are known and/or can be prepared by methods known per se (cf. DE-A-3839480, DE-A-4239296, EP-A-597360, EP-A-609734, DE-A-4303676, EP-A-617026, DE-A-4405614, US-A-5378681).
The novel substituted benzoic acid derivatives of the general formula (III) can also be obtained as follows:
reacting a halo (alkyl) benzoic acid of formula (V)
n、A、R3And R4Each as defined above, and
x represents halogen (in particular fluorine, chlorine or bromine)
With compounds of the general formula (VI)
H-Z (VI) wherein
Z is as defined above, and Z is as defined above,
the reaction is carried out at temperatures of from 50 ℃ to 200 ℃ if appropriate in the presence of reaction auxiliaries, such as triethylamine or potassium carbonate, and if appropriate in the presence of diluents, such as acetone, acetonitrile, N-dimethyl-formamide or N, N-dimethyl-acetamide (cf. preparation examples).
Instead of the halo (alkyl) benzoic acids of the formula (V), it is also possible to react the appropriate nitriles, amides and esters, in particular methyl or ethyl esters, with compounds of the formula (VI) analogously to the process described above. The corresponding substituted benzoic acids can then be obtained by hydrolysis in a conventional manner, for example by reaction with aqueous ethanol of potassium hydroxide.
The halo (alkyl) benzoic acids of the formulｃA (V) - -or the corresponding nitriles or esters- -required as precursors are known and/or can be prepared by processes known per se (cf. EP-A-90369, EP-A-93488, EP-A-399732, EP-A-480641, EP-A-609798, EP-A-763524, DE-A-2126720, WO-A-93/03722, WO-A-97/38977, US-A-3978127, US-A-4837333).
The compounds of the formula (VI) required as further precursors are known and/or can be prepared by methods known per se.
The process according to the invention for preparing novel substituted benzoylcyclohexanediones of the general formula (I) is carried out using a dehydrating agent. Suitable dehydrating agents here are the customary chemicals which are suitable for combining with water.
Examples of these compounds are dicyclohexylcarbodiimide and carbonyldiimidazole.
A particularly suitable dehydrating agent is dicyclohexylcarbodiimide.
The novel substituted benzoylcyclohexanediones of the general formula (I) are prepared, if appropriate, using reaction auxiliaries.
Examples of these compounds are sodium cyanide, potassium cyanide, acetone cyanohydrin, 2-cyano-2- (trimethylsilyloxy) propane and trimethylsilylcyanide.
A particularly suitable reaction auxiliary is trimethylsilyl cyanide.
The process according to the invention for preparing the novel substituted benzoylcyclohexanediones of the general formula (I) is, if appropriate, carried out using further reaction auxiliaries. Further reaction auxiliaries which are suitable for the process of the invention are generally basic organic nitrogen compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N-dimethylaniline, N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2, 4-dimethyl-, 2, 6-dimethyl-, 3, 4-dimethyl-and 3, 5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1, 4-diazabicyclo [ 2], 2, 2-octane (DABCO), 1, 5-diazabicyclo [ 4.3.0]-non-5-ene (DBN) or 1, 8-diazabicyclo [ 5.4.0]-undec-7-ene (DBU).
Suitable diluents for carrying out the process according to the invention are, in particular, inert organic solvents. These solvents include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride or 1, 2-dichloroethane; ethers, such as diethyl ether, isopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-formanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate; sulfoxides, such as dimethyl sulfoxide.
The reaction temperature can be carried out within a relatively wide range when carrying out the process of the invention. Generally, the reaction is carried out at a temperature of between 0 ℃ and 150 ℃, preferably between 10 ℃ and 120 ℃.
The process of the invention is generally carried out at atmospheric pressure. However, the process of the invention may also be carried out under elevated or reduced pressure, typically at a pressure between 0.1 bar and 10 bar.
In carrying out the process of the present invention, generally, approximately equimolar amounts of the starting materials are employed. However, it is also possible to employ one of the reaction components in relatively large excess. The reaction is usually carried out in a suitable diluent in the presence of a dehydrating agent and the reaction mixture is usually stirred at the desired temperature for several hours. The work-up is carried out by customary methods (cf. preparation examples).
The active compounds according to the invention can be used as defoliants, desiccants, stemicides and, in particular, as herbicides. By weeds, in their broadest sense, it is understood all plants which grow in places where they are not. Whether the substances according to the invention act as biocidal herbicides or selective herbicides depends essentially on the amount used.
The compounds of the invention may be used in connection with, for example, the following plants:
dicotyledonous weeds of the following genera: mustard, striga, Galium, Stellaria, Matricaria, Chamomilla, achyranthes, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Arthropoda, Matricaria, Hypericum, Veronica, Abutilon, Rutaceae, Viola, Murraya, Papaveris, cornflower, Trifolium, Ranunculus and Taraxacum,
dicotyledonous crops of the following genera: gossypium, glycine, beta, Daucus, phaseolus, pisum, Solanum, Linum, Ipomoea, Brassica, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, and Cucurbita,
monocotyledonous weeds of the genera: echinochloa, Setaria, Panicum, crab, echelle, Poa, Festuca, cricket, brachiaria, Lolium, Bromus, Avena, Cyperus, sorghum, Agropyron, Cynodon, Potentilla, Fimbristylis, Sagittaria, Eleocharitis, Eleocharis, Scirpus, Paspalum, duckbilled, Cytisum, Drynariae, Agrimonia, Aleurites, and efflorescence,
monocotyledonous crops of the genera: oryza, Zea, Triticum, Hordeum, Avena, Secale, sorghum, Panicum, Saccharum, Ananadis, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, and can also be extended in the same way to other plants.
Depending on the concentration of the compounds, the compounds are suitable for biocidal control of weeds, for example industrial fields and railway lines, and also roads and squares with or without plantation forests. Likewise, the compounds may be used to control weeds in perennial crops, such as forests, ornamental forests, orchards, vineyards, citrus forests, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit forests and hop fields, grasslands, stadiums and rangelands. And the compounds of the present invention may also be used to selectively control weeds in annual crops.
The compounds of formula (I) according to the invention are particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous crops both pre-and post-emergence.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspoemulsions, natural or synthetic materials impregnated with active compound, and microencapsulations in polymeric substances.
These formulations can be produced in a known manner, for example by mixing the active compounds with extenders, i.e. liquid solvents, and/or with solid carriers, and optionally using surfactants, i.e. emulsifiers and/or dispersants, and/or foam formers.
If water is used as extender, organic solvents can also be used as co-solvents. Suitable liquid solvents are mainly: aromaticcompounds, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or ethylene glycol and ethers and esters thereof, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide or dimethyl sulfoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates, suitable solid carriers for granules are: for example crushed and fractionated natural minerals such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of organic and inorganic powders, and granules of organic substances such as: sawdust, coconut shells, corn cobs and tobacco stems; suitable emulsifiers and/or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and albumin hydrolysates; suitable dispersants are: such as lignin sulfite waste liquor and methyl cellulose.
Binders such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or emulsions, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives may be mineral and vegetable oils.
It is also possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian blue, and organic dyes, for example alizarin dyes, azo dyes and metal phthalocyanine dyes, and salts of micronutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally contain from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, either as final preparations or as tank mixes.
The possible co-components of the mixture are known herbicides such as acetochlor, acifluorfen (sodium salt), aclonifen, alachlor, diclofen, amidochlomethoate, amidochlor, amidosulfuron, pyraflufen, fenflurazone, fenfluramine, fenflurazon, fenfluramine, fenflurazon, fenfluramine, fenflurazon, fenfluridone, fenflurazon, fenfluridone, fenflurazon, fenfluridone, fenflurazon, fenfluridone, fenflurazon, fenfluridone, fenflurazon, fenfluridone, fenpyr, fenflurazon, fenfluridone, fenflurazon, fenfluridone, fenpyr, fenfluridone, fenpyr, fenflurazon, fenfluridone, fenflurazon, metosul, fenfluridone, fenpyr, fenfluridone, fenpyr, fenfluridone, fenpyr, fenflurazon, fenpyr, metosul, fenflurazon, fenpyr, fenflurazon, fenpyr, fenfluridone, fenpyr, fenflurazon, fenpyr, fenfluridone, fenpyr, fenflurazon, fenpyr, fenflurazon, fenpyr, fenfluridone, fenpyr, fenflurazon, fenpyr, fenfluridone, fenflurazon, fenpyr, fenflurazon, fenfluridone, fenpyr, fenfluridone, fenflurazon, fenpyr, fenfluridone, fenpyr, fenflurazon, fenpyr, fenfluridone, fenpyr, fenflurazon, fenpyr, fenflurazon, fenpyr, fenfluridone, fenflurazon, fenpyr, fenflurazon, fenpyr, fenfluridone, fenflurazon, fenpyr.
Or else mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and soil conditioners.
The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as directly usable solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by pouring, spraying, atomizing or spreading, etc.
The active compounds according to the invention can be applied before or after germination of the plants. They may also be incorporated into the soil prior to sowing.
The amount of active compound used can vary within a relatively wide range. The amount depends essentially on the desired effect. Typically, the amount used is between 1g and 10 kg per hectare of soil surface area, preferably 5g to 5 kg per hectare.
The preparation and use of the active compounds according to the invention can be found in the following examples.
Preparation examples:
example 1
1.2g (3.48mmol) of 5-ethoxy-4-methyl-2- (2-carboxy-5-trifluoromethyl-benzyl) -2, 4-dihydro-3H-1, 2, 4-triazol-3-one are suspended in 30ml of acetonitrile and mixed at room temperature (approx. 20 ℃) with 0.39g (3.48mmol) of 1, 3-cyclohexanedione and 0.76g (3.7mmol) of Dicyclohexylcarbodiimide (DCC). The reaction mixture was stirred at room temperature overnight (about 15 hours) before being mixed with 1.0ml (7.0mmol) of triethylamine and 0.10ml (3.9mmol) of trimethylsilyl cyanide. After 3 hours at room temperature, the mixture is stirred with 100ml of 5% strength aqueous sodium carbonate solution and the separated dicyclohexylurea is filtered off with suction. The aqueous alkaline phase was extracted several times withethyl acetate. The aqueous phase was then adjusted to pH2 with 35% hydrochloric acid, after which extraction was repeated with dichloromethane. The dichloromethane phase was dried over sodium sulfate and concentrated.
This gives 0.8g (52% of theory) of 5-ethoxy-4-methyl-2- [2- (2, 6-dioxo-cyclohexyl-carbonyl) -5-trifluoromethyl-benzyl]-2, 4-dihydro-3H-1, 2, 4-triazol-3-one as an amorphous residue.
LogP (determined at pH = 2): 2.70.
example 2
A solution of 1.5g (7.2mmol) dicyclohexylcarbodiimide in 40ml acetonitrile is added to a suspension of 2.15g (6.5mmol)2- (4-carboxy-3-chloro-phenyl) -4-methyl-5-trifluoromethyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one, 0.83g (7.2mmol) 1, 3-cyclohexanedione and 40ml acetonitrile. The reaction mixture was stirred at 20 ℃ for 16 hours. Thereafter 1.3g (13mmol) of triethylamine and 0.26g (2.6mmol) of trimethylsilylcyanide are added and the reaction mixture is stirred at 20 ℃ for a further 4 hours. The mixture is then stirred with 180ml of a 2% strength aqueous sodium carbonate solution and filtered off with suction. The mother liquor was extracted with ethyl acetate. The aqueous phase is acidified with 2N hydrochloric acid and extracted with dichloromethane. The organic phase was dried, concentrated under water pump vacuum and digested with ether/petroleum ether. The resulting crystalline product was filtered off with suction.
This gives 1.6g (59% of theory) of 2- [4- (2, 6-dioxocyclohexylcarbonyl) -3-chlorophenyl]-4-methyl-5-trifluoromethyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one, m.p.182 ℃.
LogP (determined at pH = 2): 3.13.
in analogy to preparation examples 1 and 2 and in accordance with the general description of the preparation process of the invention, it is also possible to prepare, for example, the compounds of the formula (I) - -or the formulae (IA-3), (IB-2), (IC-2) or (ID) listed in tables 1 and 2 below.Table 1: examples of Compounds of formula (IA-3), (IB-2), (IC-2) 
Table 2: examples of compounds of formula (ID)
Starting material of formula (iii): example (III-1)
4.5g (15mmol) of 2- (3-chloro-4-cyano-phenyl) -4-methyl-5-trifluoromethyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one are digested with 80ml of 60% strength sulfuric acid and the mixture is heated under reflux for 6 hours. After cooling to room temperature, the resulting crystalline product is isolated by suction filtration.
This gives 4.5g (91% of theory) of 2- (3-carboxy-4-chloro-phenyl) -4-methyl-5-trifluoromethyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one, m.p. 223 ℃.
Example (III-2)
2g (4.9mmol) of 5-bromo-4-methyl-2- (2-ethoxycarbonyl-5-trifluoromethyl-benzyl) -2, 4-dihydro-3H-1, 2, 4-triazol-3-one (comparative example IV-1) are dissolved in 30ml of 10% strength aqueous potassium hydroxide solution in ethanol and heated at reflux for 2 hours. The reaction mixture was concentrated under waterpump vacuum, digested with 20ml water and acidified with dilute hydrochloric acid. The precipitated solid was filtered off and dried.
This gives 1.2g (71% of theory) of 5-ethoxy-4-methyl-2- (2-carboxy-5-trifluoromethyl-benzyl) -2, 4-dihydro-3H-1, 2, 4-triazol-3-one as solid product.
LogP:2.18a)
Example (III-3)
13.4g (35mmol) of 4-methyl-5-trifluoromethyl-2- (2, 6-dichloro-3-methoxycarbonylbenzyl) -2, 4-dihydro-3H-1, 2, 4-triazol-3-one are initially taken up in 60ml of 1, 4-dioxane and 1.54(38.5mmol) of sodium hydroxide in 20ml of water are metered in at room temperature. The reaction mixture was stirred at 60 ℃ for 150 minutes and then concentrated under water pump vacuum. The residue was dissolved in 100ml of water and the pH of the solution was adjusted to 1 by addition of concentrated hydrochloric acid. The resulting crystalline product was isolated by suction filtration.
This gives 11.7g (90% of theory) of 4-methyl-5-trifluoromethyl-2- (2, 6-dichloro-3-carboxy-benzyl) -2, 4-dihydro-3H-1, 2, 4-triazol-3-one, m.p. 207 ℃.
By the methods of examples (III-1) to (III-3), compounds of the general formula (III) such as those listed in Table 2 below can also be prepared.Table 2: examples of Compounds of formula (III)
Starting material of formula (iv): example (IV-1)
Step 1
10g (49mmol) of 2-methyl-4-trifluoromethyl-benzoic acid are dissolved in 150ml of ethanol and mixed with 1ml of concentrated sulfuric acid. The solution was heated under reflux for 24 hours, then concentrated, the residue was digested with dichloromethane and extracted with saturated aqueous sodium bicarbonate. The dichloromethane phase was dried over sodium sulfate and concentrated under waterpump vacuum.
This gives 9g (80% of theory) of ethyl 2-methyl-4-trifluoromethylbenzoate as an amorphous residue.
Step 2
9g (39mmol) of ethyl 2-methyl-4-trifluoromethyl-benzoate are dissolved in 200ml of tetra-ethyl benzoateIn methyl chloride and mixed with 7g (39mmol) of N-bromo-succinimide and 0.1g of dibenzoyl peroxide. The mixture is heated under reflux for 6 hours and the precipitated amber is filtered offThe succinimide was removed and the filtrate was concentrated under water pump vacuum.
This gives 12g of an amorphous residue which, in addition to ethyl 2-bromomethyl-4-trifluoromethyl-benzoate, contains 17% of ethyl 2, 2-dibromomethyl-4-trifluoromethyl-benzoate and 12% of ethyl 2-methyl-4-trifluoromethyl-benzoate.
Step 3
4g 2-bromomethyl-4-trifluoromethyl-benzoic acid ethyl ester (purity approx. 70%) and 2.28g (12.8mmol) 5-bromo-4-methyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one were dissolved in 150ml acetonitrile, mixed with 5.3g (38.4mmol) potassium carbonate and stirred vigorously under heated reflux for 2 hours. The reaction mixture was digested with water and extracted repeatedly with dichloromethane. The combined dichloromethane phases were dried over sodium sulfate, concentrated under waterpump vacuum and chromatographed.
This gives 2g (38% of theory) of 5-bromo-4-methyl-2- (2-ethoxycarbonyl-5-trifluoromethylbenzyl) -2, 4-dihydro-3H-1, 2, 4-triazol-3-one as amorphous product.
1H NMR(CDCl3,δ):5.46ppm。
Example (IV-2)
6.7g (40mmol) of 4-methyl-5-trifluoromethyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one are initially taken in 150ml of acetonitrile and mixed with 11g (80mmol) of potassium carbonate. The mixture was heated to 50 ℃ and then a solution of 13.1g (44mmol) of methyl 3-bromomethyl-2, 4-dichlorobenzoate in 20ml of acetonitrile was added dropwise with stirring, and the reaction mixture was heated under reflux with stirring for 15 hours. After this time, it is concentrated under waterpump vacuum and the residue is digested with dichloromethane, washed with 1N hydrochloric acid, dried over sodium sulfate and filtered. The filtrate is concentrated under reduced pressure, the residue is digested with petroleum ether and the crystalline product is isolated by suction filtration.
This gives 14.9g (97% of theory) of 4-methyl-5-trifluoromethyl-2- (2, 6-dichloro-3-methoxycarbonyl-benzyl) -2, 4-dihydro-3H-1, 2, 4-triazol-3-one with a melting point of 109 ℃.
Analogously to examples (IV-1) and (IV-2), the preparationThe following compounds of the general formula (IVa) listed in Table 3 were prepared.
Table 3: examples of Compounds of formula (IV) 
The logP given in the tables was determined by HPLC on an EECDirective 79/831 Annex V.A8 using a reverse phase column (C18). Themeasurement temperature was 43 ℃.
(a) Mobile phases for the determination in the acidic range: 0.1% phosphoric acid aqueous solution, acetonitrile; linear gradient of 10% acetonitrile to 90% acetonitrile-the corresponding data in the table are labeleda)。
(b) Mobile phase for the determination in the neutral range: 0.01 mol phosphate buffer water solution and acetonitrile; linear gradient of 10% acetonitrile to 90% acetonitrile-the corresponding data in the table are labeledb)
The calibration was carried out using unbranched alk-2-ones (having 3 to 16 carbon atoms) whose logP values were known (which were determined by retention times between two consecutive alkanones using linear interpolation).
The lambda maximum was determined as the highest peak of the chromatographic signal using a UV spectrum from 200nm to 400 nm.
Application examples
Example A
Pre-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
In the preparation of suitable active compound formulations, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
The seeds of the test plants are sown into customary soil and, approximately 24 hours later, the soil is watered with the active compound preparation and a specific amount of active ingredient is applied per unit area. The concentration of the spray liquor is chosen such that the particular amount of active compound required is applied at a spray rate of 1000 litres of water per hectare.
After three weeks, the extent of damage to the plants was compared to the development of untreated controls and% damage was determined visually.
The numerical values have the following meanings:
0% = no effect (same as untreated)
100% = complete destruction
In this test, for example, the compounds of preparation examples 1 and 10 show very strong activity against weeds, some of which are well tolerated by crops such as maize.
Table a: pre-emergence test/greenhouse
Example B
Post-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
In the preparation of suitable active compound formulations, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
The test plants having a plant height of 5 to 15 cm are sprayed with a defined amount of the desired active compound preparation per unit area. The concentration of the spray liquor is chosen such that a specific amount of the desired compound is applied in an amount of 1,000 litres water per hectare.
After three weeks, the degree of damage in the plants was compared to untreated controls, and% damage was determined.
The numerical values have the following meanings:
0% = no effect (same as untreated)
100% = complete destruction
In this test, the compounds of preparation examples 10 and 15 show very strong activity against weeds, some of which are well tolerated by crops such as maize.
Table B: post-emergence test/greenhouse
Claims (11)
1. Substituted benzoylcyclohexandions of the general formula (I)(ii) a ketone(s),
wherein
m represents the number 0, 1,2 or 3,
n represents the number 0, 1,2 or 3,
a represents a single bond or an alkanediyl (alkylene) group,
R1represents hydrogen, or represents in each case optionally substituted alkyl or alkoxycarbonyl,
R2represents optionally substituted alkyl, or with R1Together represent alkanediyl (alkylene), wherein in this case m represents 1 and R1And R2Either on the same carbon atom ("geminal") or on two adjacent carbon atoms ("vicinal"),
R3represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen or represents in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino or dialkylaminosulfonyl,
R4represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen or represents in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino or dialkylaminosulfonyl,
z represents an optionally substituted 4-to 12-membered saturated or unsaturated mono-or bicyclic heterocyclic group containing 1 to 4 heteroatoms (up to 4 nitrogen atoms and optionally- -or alternatively- -oxygen or sulfur atoms, or a SO group or SO2A group) and which additionally contains one to three oxo (C = O) and/or thioxo (C = S) groups as heterocyclic components,
including all possible tautomers of the compounds of general formula (I) and possible salts of the compounds of general formula (I).
2. Substituted benzoylcyclohexanediones according to claim 1, characterized in that,
wherein
m represents the number 0, 1 or 2,
n represents the number 0, 1 or 2,
a represents a single bond or represents an alkanediyl (alkylene) group having 1 to 4 carbon atoms,
R1represents hydrogen or optionally halogen-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulfinyl-or C1-C4-an alkylsulfonyl-substituted alkyl group having 1 to 6 carbon atoms or an alkoxycarbonyl group having up to 6 carbon atoms,
R2represents optionally halogen-substituted alkyl having 1 to 6 carbon atoms, or with R1Together represent an alkanediyl (alkylene) group having 2 to 5 carbon atoms, wherein in this case m represents 1 and R1And R2Either on the same carbon atom ("geminal") or on two adjacent carbon atoms ("vicinal"),
R3represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen or represents in each case optionally halogen-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulfinyl-or C1-C4-alkylsulfonyl-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each having up to 4 carbon atoms in the alkyl radical, or represents alkylamino, dialkylamino or dialkylaminosulfonyl, each having up to 4 carbon atoms in the alkyl radical,
R4represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen or represents in each case optionally halogen-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulfinyl-or C1-C4-alkylsulfonyl-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each having up to 4 carbons in the alkyl radical, or represents alkylamino, dialkylamino or dialkylaminosulfonyl, each having up to 4 carbon atoms in the alkyl radical,
z represents one of the following heterocyclic groups:
wherein each dotted line represents a single or double bond,
q represents oxygen or sulphur, and Q represents oxygen or sulphur,
R5represents hydrogen, hydroxyl, mercapto, cyano, halogen, each optionally substituted by halogen-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkylsulfinyl-or C1-C4-alkylsulfonyl-substituted alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl, each having up to 6 carbon atoms in the alkyl radical, represents alkylamino or dialkylamino, each optionally substituted by halogen, each having up to 6 carbon atoms in the alkyl radical, represents alkenyl, alkynyl, alkenyloxy, alkenylthio or alkenylamino, each optionally substituted by halogen, represents cycloalkyl, cycloalkylalkyl, cycloalkyloxy, cycloalkylthio or cycloalkylamino, each optionally substituted by halogen, each having 3 to 6 carbon atoms in the cycloalkyl radical and optionally having up to 4 carbon atoms in the alkyl moiety, or represents each optionally substituted by halogen, C1-C4-alkyl-or C1-C4-alkoxy-substituted phenyl, phenoxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or benzylamino, and
R6represents hydrogen, hydroxyl, amino, (1,1-) alkyleneamino having up to 4 carbon atoms, each optionally substituted by halogen-or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylamino, dialkylamino or alkanoylamino each having up to 6 carbon atoms in the alkyl radical, represents alkenyl, alkynyl or alkenyloxy each optionally substituted by halogen, each having up to 6 carbon atoms in the alkenyl or alkynyl radical, represents each optionally substituted by halogen, each having 3 to 6 carbon atoms in the cycloalkyl radicalAnd cycloalkyl, cycloalkylalkyl or cycloalkylamino optionally having up to 3 carbon atoms in the alkyl moiety, or represents each optionally substituted by halogen-, C1-C4-alkyl-or C1-C4-alkoxy-substituted phenyl or benzyl, or with an adjacent group R5Or R6Together represent optionally halogen-or C1-C4-alkyl-substituted alkanediyl having 3 to 5 carbon atoms, or-in two adjacent radicals R5And R5In the case of a double bond- -with an adjacent radical R5Together also represent a benzo group.
3. Substituted benzoylcyclohexanediones according to claim 1, characterized in that,
m represents the number 0, 1 or 2,
n represents the number 0, 1 or 2,
a represents a single bond, methylene, ethylene (ethyl-1, 1-diyl) and dimethylene (ethyl-1, 2-diyl),
R1represents hydrogen, represents methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, each optionally substituted by fluorine-, chlorine-, methoxy-, ethoxy-, n-or i-propoxy-, methylthio-, ethylthio-, n-or i-propylthio-, methylsulfinyl-, ethylsulfinyl-, n-or i-propylsulfinyl-, methylsulphonyl-, ethylsulphonyl-, n-or i-propylsulphonyl-, or represents methoxycarbonyl, ethoxycarbonyl, n-or i-propoxycarbonyl,
R2represents methyl, ethyl, n-or i-propyl, or with R1Together represent methylene, ethylene-1, 1-diyl (ethylene, -CH (CH)3) -), ethane-1, 2-diyl (dimethylene, -CH2CH2-), propane-1, 3-diyl (trimethylene group, -CH2CH2CH2-), but-1, 4-diyl (tetramethylene, -CH)2CH2CH2CH2-) or penta-1, 5-diyl (pentamethylene, -CH2CH2CH2CH2CH2-, where in this case m represents 1 and R1And R2Is located in a phaseThe same carbon atom ("gem") and on an adjacent carbon atom ("vicinal"),
R3represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, represents methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl which are in each case optionally substituted by fluorine and/or chlorine-, methoxy-, ethoxy-, n-or i-propoxy-, methylthio-, ethylthio-, n-or i-propylthio-, methylsulfinyl-, ethylsulfinyl-, methylsulphonyl-or ethylsulphonyl-, represents methoxy, ethoxy, n-or i-propoxy which are in each case optionally substituted by fluorine and/or chlorine-, methoxy-, ethoxy-, n-or i-propoxy-, represents methylthio, which is in each case optionally substituted by fluorine and/or chlorine, Ethylthio, n-or isopropylthio, methylsulfinyl, ethylsulfinyl, n-or isopropylsulfinyl, methylsulfonyl, ethylsulfonyl, n-or isopropylsulfonyl or represents methylamino, ethylamino, n-or isopropylamino, dimethylamino, diethylamino, dimethylaminosulfonyl or diethylaminosulfonyl,
R4represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, represents methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, each of which is optionally substituted by fluorine and/or chlorine-, methoxy-, ethoxy-, n-or i-propoxy-, methylthio-, ethylthio-, n-or i-propylthio-, methylsulfinyl-, ethylsulfinyl-, methylsulphonyl-or ethylsulphonyl-, represents methyl, ethyl, n-or i-propyl, each of which is optionally substituted by fluorine and/or chlorine-, methoxy-, s-or t-butyl-, ethoxy-, n-or isopropoxy-substituted methoxy, ethoxy, n-or isopropoxy, represents methylthio, ethylthio, n-or isopropylthio, methylsulfinyl, ethylsulfinyl, n-or isopropylsulfinyl, methylsulfonyl, ethylsulfonyl, n-or isopropylsulfonyl, each optionally substituted by fluorine and/or chlorine, or represents methylamino, ethylamino, n-or isopropylamino, dimethylamino, diethylamino, dimethylaminosulfonyl or diethylaminosulfonyl,
z represents the following heterocyclic group
Wherein the dotted line in each case denotes a single or double bond,
q represents oxygen or sulphur, and Q represents oxygen or sulphur,
R5represents hydrogen, hydroxyl, mercapto, cyano, fluorine, chlorine, bromine, iodine, represents methyl, ethyl, n-or i-propyl, sec-or i-butyl, methylsulfinyl, ethylsulfinyl, n-or i-propylsulfinyl, methylsulphonyl, ethylsulphonyl, n-or i-propylsulphonyl-substituted methyl, ethyl, n-or i-propyl, n-, i-, sec-or t-butyl, methoxy, ethoxy, n-or i-propoxy, n-, i-, sec-or t-butoxy, methylthio, methyl,ethyl, n-or i-propylsulfonyl, n-or i-butyloxy, n-or i-propyloxy, ethylthio, n-or isopropylthio, n-, i-, s-or t-butylthio, methylsulfinyl, ethylsulfinyl, n-or i-propylsulfinyl, methylsulphonyl, ethylsulphonyl, n-or i-propylsulphonyl, or represents methylamino, ethylamino, n-or i-propylamino, n-, i-, s-or t-butylthioAmino, dimethylamino, diethylamino, di-n-propylamino or diisopropylamino, represents in each case optionally fluorine-and/or chlorine-substituted ethenyl, propenyl, butenyl, ethynyl, propynyl, butynyl, propenyloxy, butenyloxy, propenylthio, propenylamino or butenylamino, represents in each case optionally fluorine-and/or chlorine-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino or cyclohexylamino, or represents in each case optionally fluorine-, chlorine-, methyl-, or cyclohexylamino, Ethyl-, n-or i-propyl-, n-, i-, s-or t-butyl-, methoxy-, ethoxy-, n-or i-propoxy-substituted phenyl, phenoxy, phenylthioA group selected from the group consisting of a phenylamino group, a benzyl group, a benzyloxy group, a benzylthio group and a benzylamino group,
R6represents hydrogen, hydroxy, amino, represents methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, methoxy, ethoxy, n-or i-propoxy, methylamino, ethylamino or dimethylamino, each of which is optionally substituted by fluorine and/or chlorine, represents vinyl, propenyl, ethynyl, propynyl or propenyloxy, represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally substituted by fluorine and/or chlorine, or represents methyl, ethyl, n-or i-propyl, n-substituted, Iso-, sec-or tert-butyl-, methoxy-, ethoxy-, n-or isopropoxy-substituted phenyl or benzyl, or R adjacent thereto5Or R6Together represent each optionally methyl-and/or ethyl-substituted propane-1, 3-diyl (trimethylene) or butane-1, 4-diyl (tetramethylene), or-at two adjacent R5And R5In the case of a double bond- -to an adjacent radical R5Together also represent a benzo group.
4. Substituted benzoylcyclohexanediones according to claim 1, characterized in that the compounds of the general formula (IA),wherein
m represents 0, 1 or 2,
n represents 0, 1 or 2,
a represents a single bond or a methylene group,
q represents oxygen or sulphur, and Q represents oxygen or sulphur,
R1represents hydrogen, methyl, ethyl, n-or isopropyl,
R2represents a methyl group, and a salt thereof,
R3represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulphonylmethyl, methoxy, ethoxy, difluoromethoxyTrifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl,
R4represents nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulphonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl or dimethylaminosulphonyl,
R5represents methyl, ethyl, n-or i-propyl, trifluoromethyl, methoxy, ethoxy, n-or i-propoxy, methylthio, ethylthio, n-or i-propylthio, methylsulfinyl, ethylsulfinyl, n-or i-propylsulfinyl, methylsulphonyl, ethylsulphonyl, n-or i-propylsulphonyl, or represents cyclopropyl,
R6represents methyl, ethyl, methoxy, ethoxy or cyclopropyl.
5. Substituted benzoylcyclohexanediones according to claim 1, characterized in that the compounds of the general formula (IB),
wherein
m represents 0, 1 or 2,
n represents 0, 1 or 2,
a represents a single bond or a methylene group,
q represents oxygen or sulphur, and Q represents oxygen or sulphur,
R1represents hydrogen, methyl, ethyl, n-or isopropyl,
R2represents a methyl group, and a salt thereof,
R3represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulphonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonylA radical or a dimethylaminosulfonyl radical,
R4represents nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulphonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl or dimethylaminosulphonyl,
R5represents methyl, ethyl, n-or i-propyl, trifluoromethyl, methoxy, ethoxy, n-or i-propoxy, methylthio, ethylthio, n-or i-propylthio, methylsulfinyl, ethylsulfinyl, n-or i-propylsulfinyl, methylsulphonyl, ethylsulphonyl, n-or i-propylsulphonyl, or represents cyclopropyl,
R6represents methyl, ethyl, methoxy, ethoxy or cyclopropyl.
6. Substituted benzoylcyclohexanediones according to claim 1, characterized in that the compounds of the general formula (IC),
wherein
m represents 0, 1 or 2,
n represents 0, 1 or 2,
a represents a single bond or a methylene group,
q represents oxygen or sulphur, and Q represents oxygen or sulphur,
R1represents hydrogen, methyl, ethyl, n-or isopropyl,
R2represents a methyl group, and a salt thereof,
R3represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulphonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl or dimethylaminosulphonyl,
R4represents nitro, cyano, fluorine, chlorine,Bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl,
R5represents methyl, ethyl, n-or i-propyl, trifluoromethyl, methoxy, ethoxy, n-or i-propoxy, methylthio, ethylthio, n-or i-propylthio, methylsulfinyl, ethylsulfinyl, n-or i-propylsulfinyl, methylsulphonyl, ethylsulphonyl, n-or i-propylsulphonyl, or represents cyclopropyl,
R6represents methyl, ethyl, methoxy, ethoxy or cyclopropyl.
7. Substituted benzoylcyclohexanediones according to any of claims 1 to 6, characterized in that the salts thereof are sodium, potassium, magnesium, calcium, ammonium, C1-C4Alkyl ammonium, di- (C)1-C4Alkyl) -ammonium, tri- (C)1-C4Alkyl) -ammonium, tetra- (C)1-C4-alkyl) -ammonium, tri- (C)1-C4-alkyl) -sulfonium, C5Or C6Cycloalkylammonium and di- (C)1-C2-alkyl) -benzylammonium salts.
8. A process for preparing substituted benzoylcyclohexanediones according to any of claims 1 to 6, characterized in that 1, 3-cyclohexanediones of the general formula (II) or derivatives thereof are reacted, if appropriate in the presence of a dehydrating agent, if appropriate in the presence of one or more reaction auxiliaries and if appropriate in the presence of a diluent
Whereinm、R1And R2Each as defined in any one of claims 1 to 6 with substituted benzoic acids of the general formula (III)Wherein
n、A、R3、R4And Z are each as defined in claimAs defined in any one of claims 1 to 6,
and, if appropriate, the compounds of the formula (I) obtained in this way are subsequently subjected to electrophilic or nucleophilic or oxidation or reduction reactions in the range defined by the substituents by customary methods or are converted into salts by customary methods.
9. Substituted benzoic acids of the general formula (III)
Wherein
n、A、R3、R4And Z are each as defined in any one of claims 1 to 6,
except for the compounds 2- (5-carboxy-2, 4-dichloro-phenyl) -4-difluoromethyl-5-methyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one and 2- (5-carboxy-2, 4-dichloro-phenyl) -4, 5-dimethyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one.
10. Use of at least one substituted benzoylcyclohexanedione according to any one of claims 1 to 6 for controlling undesired vegetation.
11. Herbicidal composition, characterized in that it comprises at least one substituted benzoylcyclohexanedione according to any of claims 1 to 6 and a conventional extender.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833360.9 | 1998-07-24 | ||
| DE19833360 | 1998-07-24 | ||
| DE19921732.7 | 1999-05-11 | ||
| DE19921732A DE19921732A1 (en) | 1998-07-24 | 1999-05-11 | New 2-benzoyl-1,3-cyclohexanedione derivatives useful as herbicides, especially for selective weed control in monocot crops, e.g. maize |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200410068519XA Division CN1597672A (en) | 1998-07-24 | 1999-07-13 | Substituierte benzoylcyclohexandione |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1310714A true CN1310714A (en) | 2001-08-29 |
| CN1177835C CN1177835C (en) | 2004-12-01 |
Family
ID=26047675
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200410068519XA Pending CN1597672A (en) | 1998-07-24 | 1999-07-13 | Substituierte benzoylcyclohexandione |
| CNB998090344A Expired - Fee Related CN1177835C (en) | 1998-07-24 | 1999-07-13 | Substituted benzoylcyclohexandiones |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200410068519XA Pending CN1597672A (en) | 1998-07-24 | 1999-07-13 | Substituierte benzoylcyclohexandione |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US6924251B1 (en) |
| EP (1) | EP1100789B1 (en) |
| JP (1) | JP2002521373A (en) |
| CN (2) | CN1597672A (en) |
| AT (1) | ATE288900T1 (en) |
| AU (1) | AU749204B2 (en) |
| BR (1) | BR9912392A (en) |
| CA (1) | CA2338304A1 (en) |
| DK (1) | DK1100789T3 (en) |
| ES (1) | ES2237141T3 (en) |
| PL (1) | PL345561A1 (en) |
| WO (1) | WO2000005221A1 (en) |
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| CN103025718A (en) * | 2010-11-19 | 2013-04-03 | 中国中化股份有限公司 | Nitrogen heterocyclic substituted benzoyl compound and use thereof |
| CN112094243A (en) * | 2019-09-03 | 2020-12-18 | 山东先达农化股份有限公司 | Compound containing benzotriazine structure, preparation method and application thereof, and herbicide |
| CN112300092A (en) * | 2019-07-31 | 2021-02-02 | 东莞市东阳光农药研发有限公司 | Heterocyclic alkyl substituted dichlorobenzoyl compound and application thereof |
| CN117247363A (en) * | 2023-11-17 | 2023-12-19 | 山东滨农科技有限公司 | Oxadiazolone compound, weeding composition and application thereof |
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| DE102008060967A1 (en) * | 2008-12-06 | 2010-06-10 | Bayer Schering Pharma Aktiengesellschaft | Substituted phenylsulfonyltriazolones and their use |
| DE102010001064A1 (en) | 2009-03-18 | 2010-09-23 | Bayer Schering Pharma Aktiengesellschaft | Substituted 2-acetamido-5-aryl-1,2,4-triazolones and their use |
| PE20130683A1 (en) | 2010-02-27 | 2013-06-20 | Bayer Ip Gmbh | BISARYLL-LINKED ARYLTHRIAZOLONES AND THEIR USE |
| DE102010040187A1 (en) | 2010-09-02 | 2012-03-08 | Bayer Schering Pharma Aktiengesellschaft | Substituted N-phenethyl-triazolone acetamides and their use |
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- 1999-07-13 WO PCT/EP1999/004929 patent/WO2000005221A1/en active IP Right Grant
- 1999-07-13 CA CA002338304A patent/CA2338304A1/en not_active Abandoned
- 1999-07-13 AU AU55050/99A patent/AU749204B2/en not_active Ceased
- 1999-07-13 EP EP99941423A patent/EP1100789B1/en not_active Expired - Lifetime
- 1999-07-13 PL PL99345561A patent/PL345561A1/en unknown
- 1999-07-13 AT AT99941423T patent/ATE288900T1/en not_active IP Right Cessation
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- 1999-07-13 CN CNA200410068519XA patent/CN1597672A/en active Pending
- 1999-07-13 CN CNB998090344A patent/CN1177835C/en not_active Expired - Fee Related
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| CN103025718A (en) * | 2010-11-19 | 2013-04-03 | 中国中化股份有限公司 | Nitrogen heterocyclic substituted benzoyl compound and use thereof |
| CN103025718B (en) * | 2010-11-19 | 2016-01-20 | 中国中化股份有限公司 | Cyclosubstituted benzoyl compounds of nitrogen-containing hetero and uses thereof |
| CN112300092A (en) * | 2019-07-31 | 2021-02-02 | 东莞市东阳光农药研发有限公司 | Heterocyclic alkyl substituted dichlorobenzoyl compound and application thereof |
| WO2021018135A1 (en) * | 2019-07-31 | 2021-02-04 | 东莞市东阳光农药研发有限公司 | Heterocyclyl alkyl substituted dichlorobenzoyl compounds and applications thereof |
| CN112094243A (en) * | 2019-09-03 | 2020-12-18 | 山东先达农化股份有限公司 | Compound containing benzotriazine structure, preparation method and application thereof, and herbicide |
| CN112094243B (en) * | 2019-09-03 | 2022-03-01 | 山东先达农化股份有限公司 | Compound containing benzotriazine structure, preparation method and application thereof, and herbicide |
| CN117247363A (en) * | 2023-11-17 | 2023-12-19 | 山东滨农科技有限公司 | Oxadiazolone compound, weeding composition and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9912392A (en) | 2001-05-08 |
| EP1100789A1 (en) | 2001-05-23 |
| PL345561A1 (en) | 2001-12-17 |
| US6924251B1 (en) | 2005-08-02 |
| EP1100789B1 (en) | 2005-02-09 |
| ES2237141T3 (en) | 2005-07-16 |
| CN1597672A (en) | 2005-03-23 |
| JP2002521373A (en) | 2002-07-16 |
| AU5505099A (en) | 2000-02-14 |
| DK1100789T3 (en) | 2005-05-23 |
| WO2000005221A1 (en) | 2000-02-03 |
| CA2338304A1 (en) | 2000-02-03 |
| CN1177835C (en) | 2004-12-01 |
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| AU749204B2 (en) | 2002-06-20 |
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